Phosphate-free carboxylate-sulfate detergents

ABSTRACT

Detergent-active materials having low fish toxicity suitable for heavy duty laundering in the absence of builders comprising sulfated glycol or polyglycol half esters of alkyl or alkenyl succinic acids, or water-soluble salts thereof, wherein the alkyl or alkenyl group contains from about 14 to about 22 carbon atoms, the glycol moiety of the ester contains from 1 to 4 units of 2 to 4 carbon atoms, and the sulfate group is terminally attached to the glycol or polyglycol chain.

United States Patent [191 Danzik et al.

[ Dec. 16, 1975 PHOSPHATE-FREE I CARBOXYLATE-SULFATE DETERGENTS [75] Inventors: Mitchell Danzik, Pinole; Ralph House, El Sobrante, both of Calif.

[73] Assignee: Chevron Research Company, San Francisco, Calif.

[22] Filed: July 11, 1974 [21] Appl. No.: 483,496

Related US. Application Data [62] Division of Ser. No. 259,924, June 5, 1972, Pat. No.

[52] US. Cl. 260/458 [51] Int. Cl. C07C 141/02 [58] Field of Search 260/458 [56] References Cited UNITED STATES PATENTS 3,086,043 4/1963 Gaertner 260/513 R 3,689,532 9/1972 Emmons et al. 260/458 Primary Examiner-James 0. Thomas, Jr.

Assistant Examiner-Nicky Chan Attorney, Agent, or Firm-G. F. Magdeburger; John Stoner, Jr.; J. T. Brooks [57] ABSTRACT Detergent-active materials having low fish toxicity suitable for heavy duty laundering in the absence of builders comprising sulfated glycol or polyglycol half esters of alkyl or alkenyl succinic acids, or watersoluble salts thereof, wherein the alkyl or alkenyl group contains from about 14 to about 22 carbon atoms,-the glycol moiety of the ester contains from 1 to 4 units of 2 to 4 carbon atoms, and the sulfate group is terminally attached to the glycol or polyglycol chain.

4 Claims, No Drawings PHOSPHATE-FREE CARBOXYLATE-SULFATE DETERGENTS This is a division of application Ser. No. 259,924, filed June 5, 1972, now US. Pat. No. 3,843,707.

BACKGROUND OF THE INVENTION This application is directed to detergent active materials which may be incorporated into detergent formulations which are capable of being used for heavy duty laundering without the presence of either eutrophication-causing or highly alkaline materials which are harmful to human tissue. In addition, these detergentactive materials possess other virtues, the combination of which is unique in the detergent area. Thus the compounds are both aerobically and microaerophilically biodegradable and possess low (exceptionally low with certain species of the compounds) fish toxicity properties.

As is well known, in the United States accelerated concern for the protection of the environment has resulted in efforts by the concerned branches of Govemment and the detergent industry to eliminate phosphate builders from detergent compositions because of the fear of suspected eutrophication believed to be caused by the phosphates in the currently used detergent formulations. The precipitous introduction and marketing of many hurriedly formulated phosphatefree compositions has, however, raised the spectre of the cure being possibly worse than the illness due to the caustic nature of many of the formulations. The necessity of including some builder in the formulations as a replacement for the phosphates in order to achieve sufficient detergency has resulted in these formulations being compounded with such materials as meta-silicates and carbonates making the danger of skin, eye, and mucous membrane damage to persons who use the formulations a substantial one. Thus the Federal govemment has required that several of the new detergent formulations be labeled as hazardous substances and the Surgeon General of the United States has recently recommended that housewives continue to use phosphate-containing detergents for the present as being the lesser of evils.

In addition to the corrosive properties of many of the new detergent formulations, despite claims to the contrary, many of them have not proved to be effective replacements for conventional heavy duty detergents in terms of their ability to remove soil from fabrics and provide clean-appearing clothes, etc.

An additional problem with most conventional deter gents and which exists as well with most of the newly introduced nonphosphate detergent compositions is the fact that while they may be aerobically biodegradable with secondary disposal plants, they are not easily degradable under microaerophilic conditions such as are encountered in areas where septic tanks and cesspools provide the means of sewage disposal. This re- 'sults in substantial quantities of undegraded surface-active materials being discharged into water sources and has resulted in certain areas in Government bans on all laundering agents except for soap. 1

There exists, therefore, a pressing need for detergentactive materials which may be compounded without phosphate builders and without caustic builders, which are biodegradable and are degradable under conditions encountered in septic tanks and cesspools and which will have minimal effect on marine organisms if discharged by design or accident into rivers and lakes, etc. Thus the detergent actives should not exhibit high toxicity to fish, etc.

PRIOR ART US. Pat. No. 3,086,043 discloses as surface active materials compounds of the formula in which R is alkenyl of 8 to 20 carbons (preferably branched), R is lower alkyl of l to 4 carbon atoms or hydrogen, x is 0 to 3, and Z is a salt forming cation. The compounds are formed by reacting a hydroxy-containing sulfonate such as sodium isethionate with alkenyl succinic anhydride.

SUMMARY OF THE INVENTION Detergent active materials capable of being formulated into compositions which are suitable for heavy duty laundering in the absence of phosphate builders or such highly caustic building materials as carbonates, meta-silicates, etc., are provided. The detergent active materials are easily biodegraded, both aerobically and microaerophilically, and certain compounds display surprisingly low toxicity to marine organisms. The detergent actives are sulfated glycol or polyglycol half esters of alkyl or alkenyl succinic acids or water-soluble salts thereof, wherein the alkyl or alkenyl group contains from about 14 to about 22 carbon atoms and the glycol moiety of the ester contains from 1 to 4 units of 2 to 4 carbon atoms and the sulfate group is terminally attached to the glycol or polyglycol chain. The preferred glycol units contain two carbon atoms.

While the compounds disclosed above have good detergency and low fish toxicity levels consonant with most of the available detergents such as linear alkylbenzene sulfonate, a preferred embodiment of the invention having, along with excellent detergency, surprisingly low fish toxicity levels is represented by the class of compounds of the following formula:

in which R, and R are substantially linear saturated or unsaturated aliphatic groups of 2 to 19 carbon atoms, R is alkylene of 2 to 4 carbon atoms, 14, v, x and y are 0 or 1, z is an integer l to 4, M is H or a water-soluble salt-forming cation, the sum of the carbon atoms in R and R from about 13 to 21 carbon atoms, the sum of unsaturated sites in R and R is0 to l, the sum of u and vis l,the sumofxandyis l,andthe sumofuandx is 1.

Thus the preferred compounds are preferably derived' from hydrocarbyl succinic anhydrides wherein the attachment of the succinic moiety to the hydrocarbyl group is at carbon atoms other than the l and 2 carbon atoms of the hydrocarbyl chain. Such attachment as used in this application is defined as central attachment. Bonding at carbon atoms 1 and 2 of the hydrocarbyl group is defined as end attachment.

In an additional preferred embodiment z is an integer of l to 3, preferably 1 to 2, most preferably 2, and R is ethylene. It is further preferred that the sum of carbon atoms in R and R is from to 17. Thus, the preferred materials are sulfate salts of half esters produced by reacting ethylene glycol or diethylene glycol with an alkyl or alkenyl succinic anhydride having 16 to 18 carbon atoms in the side chain. The diethylene glycol derivative is most preferred as is the alkyl derivative.

The hydrocarbyl radicals illustrated in the formula by R R CH include such groups as tetradecyl, pentadecyl, hexadecyl, heneicosyl, docosyl, tetradecenyl, pentadecenyl, hexadecenyl, heneicosenyl and docosenyl.

Typical compounds illustrating R R and R are listed as follows:

DESCRIPTION OF THE PREFERRED EMBODIMENTS The salt-forming cation M may be any of numerous materials such as alkali metal, alkaline earth metal, ammonium, or various organic cations. Examples of suitable organic cations include nitrogen-containing organic cations such as diethanolammonium and triethanolammonium cations. The alkali metal cations are preferred, and sodium ions are particularly preferred.

The alkyl and alkenyl groups which are attached to the succinic moiety may be branched or linear, although the substantially linear materials are preferred. By substantially linear is meant that the presence of a random methyl group, for example, somewhere on the chain will not be detrimental to their ability to be degraded. The preferred alkyl groups thus include the linear alkyl from tetradecyl to docosyl and the alkenyl groups will likewise be the linear materials from tetradecenyl to docosenyl.

The succinic anhydride precursors are preferably derived by the alkylation of maleic anhydride with a monoolefin to form alkenyl succinic anhydride followed in the case of the alkyl substituted materials by hydrogenation. The olefins may be derived from any source, examples being those derived from the cracking of waxes (alpha olefins) or those derived by dehydrogenation or halogenation-dehydrohalogenation of appropriate parafiin fractions. From a commercial The alkenyl materials may be converted to alkyl succinic anhydrides by conventional hydrogenation techniques. Alternatively and preferably, the hydrogenation is carried out with the half ester. Hydrogenation may thus be carried out in the presence of conventional catalysts such as platinum, platinum on inert supports, palladium, etc.

The alkenyl or alkyl succinic anhydride is reacted with an appropriate quantity of a lower glycol or lower polyglycol to yield the half ester. An approximately stoichiometric amount of the glycol or polyglycol will cleave the anhydride ring to form the desired compound having a free carboxyl group and a hydroxyl group on the glycol or polyglycol portion of the molecule. The use of an excess of the glycol is preferred.

Sulfation of the glycol substituted half ester to produce the acid precursor of the compound is accomplished by any appropriate sulfation method, such as with oleum, sulfuric acid, or chlorosulfonic acid.

The mixed carboxylic, sulfuric acid produced is reacted with an appropriate base in order to give the detergent-active salt which then may be compounded to form the desired detergent composition.

The preferred detergents contain one or two ethylene glycol units. Fish show markedly high tolerance to these materials. In addition, the preferred compounds contain a succinic moiety which is centrally attached on the hydrocarbyl chain.

The glycols which are precursors of the preferred compounds are represented by the formula in which Y is H or a water-soluble salt-forming cation, p is l to 4, R and R are substantially linear saturated or unsaturated, unsubstituted aliphatic groups of 2 to 19 carbon atoms, R is alkylene of 2 to 4 carbon atoms, u, v, x and y are 0 or 1, the sum of the carbon atoms in R and R is from 13 to 21 carbon atoms, the sum of the unsaturated sites in R and R is 0 to l, the sum of u and v is l, the sum ofx and y is l, and the sum ofu and x is 1. In the preferred precursor the sum of the carbon atoms in R and R is 15-17, and p is l to 2, preferably 2; and R and R are alkyl.

The following examples illustrate the preparation of the detergent active materials of this invention.

EXAMPLE 1 Preparation of Octadecenyl Succinic Anhydride 9.08 Kg. (36.0 moles) of isomerized linear octadecene and 1.96 kg. (20.0 moles) of maleic anhydride were charged to a pressure vessel. The stirred mixture was heated under 30 psi of nitrogen for 6 hours at 230C. After the mixture cooled, it was transferred to a distillation apparatus and distilled, boiling point 430450F. at 0.1-0.2 mrn/I-Ig. A 93% yield of octadecenyl succinic anhydride was obtained. The product had the following isomer distribution as determined by vapor phase chromatography:

lsomer Percent Z-attachment 4.5 3-attachment 6.4 4-attachment l 1 S-attachment l 6,7,8,9-attachment 59.3

This represents a product having 95.5% central attachment.

EXAMPLE 2 Hydrogenation of Octadecenyl Succinic Anhydride G. (0.057 moles) of octadecenyl succinic anhydride, 114 g. of n-hexane and 1 g. of 5% palladium on carbon were charged to a pressure vessel. The mixture was stirred and heated to 50C. The initial hydrogen pressure was 60 psi. When the pressure dropped to 50-50 psi, the system was represented to 60 psi. This process was repeated until the hydrogen uptake essentially ceased. The mixture was filtered and the hexane was evaporated. 19.7 G. (98.5% yield) of crude octadecyl succinic anhydride was recovered.

1 EXAMPLE 3 Preparation of Diethylene Glycol Half Ester of Octadecenyl Succinic Acid 238.0 G. of diethylene glycol (2.25 moles) and 26.3 g. of a linear octadecenyl succinic anhydride (0.0747 mole) prepared as in Example 1 was placed in a vessel and stirred and heated rapidly to 150-160C. The solution was maintained at that temperature for 1 hour, then it was cooled to room temperature. A 250-ml. portion of ether was added, and the layers were separated. Then 250 ml. of ether and 125 ml. of water were added to the glycol layer. After extraction, the layers were separated.

Each of the ether layers was extracted three times with about 100 ml. portions of water. The ether layers were combined, dried over sodium sulfate, filtered and evaporated to give 34.1 g. of product. This represented a 99% yield of the diethylene glycol half ester.

EXAMPLE 4 Preparation of Ethylene Glycol Half Ester of Octadecenyl Succinic Anhydride The procedure of Example 3 was repeated with the exception that 177 g. of ethylene glycol (2.86 moles) and 25.0 g. of octadecenyl succinic anhydride (0.0714 mole) were employed. The yield of product was 95%.

EXAMPLE 5 Hydrogenation of Diethylene Glycol Half Ester of Octadecenyl Succinic Anhydride 9.12 G. (0.02 mole) of a diethylene glycol half ester of octadecenyl succinic acidwas dissolved in 42 ml. of n-hexane in a hydrogenation vessel. 1 g. of 5% palladium on carbon was added. The mixture was magnetically stirred and heated in a 50C. water bath. The initial hydrogen pressure was 60 psi. When the pressure dropped to -40 psi, the system was repressured to 60 psi. This process was repeated until the theoretical hydrogen uptake was obtained. The mixture was then filtered and the hexane was evaporated. 14.9 g. (99% yield) of diethylene glycol half ester of octadecyl succinic acid was recovered. Infrared and nuclear magnetic resonance analysis were consistent with the assigned structure and showed that the product was completely saturated.

EXAMPLE 6 Sulfation of the Diethylene Glycol Half Ester of Octadecyl Succinic Acid 2.13 G. (0.00465 mole) of the diethylene glycol half ester of Octadecyl succinic acid was dissolved in 100 ml. of dry ether. A 4.44 g. portion (0.0381 mole) of chlorosulfonic acid was added dropwise at a rapid rate. The temperature of the reaction mixture was kept at l015C. during the addition of the acid. When all of the acid was added, the cooling bath was removed, and the solution was allowed to warm to room temperature over a period of 20-30 minutes.

Sufficient 0.5 N NaOH was added to about 75 ml of water to bring the pH to ll-12. The solution was cooled to 510C., and the pH was maintained between 8 and 12 by alternate addition of the acid-containing ether solution and 0.5 N NaOH. At a final pH of 8.5, the mixture was partially evaporated to remove ether. The remaining solution was diluted to a known volume. An aliquot was taken for a Hyamine titration, and the amount of active sulfate was determined. The yield of disodium salt of sulfated diethylene glycol half ester of octadecyl succinic acid was 87%.

TABLE I DlSODlUM SALTS 0F EX. SULFATED DIETHYLENE YIELD CENTRAL NO. GLYCOL HALF-ESTERS OF: ATTACH.

8 Hexadecyl 93 95 9 Hexadecyl 94 0 l0 Heptadecyl 89 91 1 1 Nonadecyl 86 94 12 Pentadecenyl 13 Hexadecenyl 84 95 I4 He xadecenyl 72 0 l5 Heptadecenyl 86 91 16 Octadecenyl 95 17 Nonadecenyl 73 94 I8 Eicosenyl 83 19 G -C (saturated) 89 94 2O C -C (unsaturated) 93 2| C C (unsaturated) (Est.) 22 C -,C (unsaturated) 93 23 C, C (unsaturated) 93 24 l-lexadecyl 95 25 Heptadecyl 9I 26 Octadecyl 9] 27 Octadecyl 96 75 28 Octadecyl 97 0 29 Nonadecyl 92 94 30 Eicosyl 83 31 He ptadecenyl 91 32 Nonadecenyl 94 33 Eicosenyl 83 34 C -C (saturated) m 93 35 C C, (unsaturated) 93 36 C, C (unsaturated) 93 A blend of approximately equal amounts of each isomer.

A blend having a ratio of 30:40:30 for isomers of increasing molecular weight,

respectively.

m A blend having a ratio of 26:29:27: 18 for isomers of increasing molecular weight,

respectively.

EXAMPLE 37 Drying of Disodium Salt of the Half Ester of C -C Alkyl Succinic Acid 7 8 The sulfation products contain varying amounts of tions, the results can be accurately correlated. The two by-products in the range of about 1 to 20%. The alkestandard solutions are identical in formulation but are nyl derivatives have the greater quantity of by-proemployed at different hardnesses.

ducts, about 10 to 20%, whereas the alkyl derivatives have lesser amounts, about 1 to 10%. These by-products may be removed by various purification prof I cesses such as extraction, chromatography, etc., but in Welgh the present examples they were left in the products Linear All ylbenzene sulfonate (LAS) 20 because these by-products will normally be present in tPdYPlwsPhate commercial materials made in accordance with this sodium Sulfat 24 invention. Consequently, detergency and toxicity mea- Sodium Silicate 7 Carboxymethylcellulose 1 surements reported herein are representative of potential commercial products. Each product was analyzed for detergent active material by the method of House and Darragh, AnLChem., 26, 1.492 (1954). Test samples were prepared for fish toxicity measurements and for detergency effectiveness using the previously determined surface active values for determining test concentrations.

Detergency of the compounds of the present invention is demonstrated by a miniature Terg-O-Tometer test. In this test the effectiveness of the detergents is measured by their ability to remove natural sebum soil from cotton cloth. By this method, small swatches of cloth, soiled by rubbing over face and neck, are washed The standard exhibiting high detersive characteristics (Control B) is prepared by dissolving the above formulation (1.0 g.) in 1 liter of 50 ppm hard water (calculated as two-third calcium carbonate and one-third magnesium carbonate). The low detersive standard 20 (Control A) contained the formulation (1.0 g.) dissolved in one liter of 180 ppm water (same basis).

1": Cmm-ol A DR 2. R 2 4 I Cmm-nl B m CmuroI A with test solutions of detergents in a miniature labora- A further refinement in the determination of relative tory washer. The washer employed is so constructed detergency g was deVeIOPed- In this m that two standard formulations and two test formula- Stead of p y g two Standard formulahohs, (me Of tions can be used t w h diff t parts of h same the formulations used as one of the four test solutions soiled swatch. This arrangement ensures that all formuhad a known relative detergency rating which lations are working on identical soil. The quantity of had been determined y the above formula- Relative il removed b thi hi proeedure i d i d detergency ratings of the other three formulations were b measuring th refleetanees f h new l h, h then determined by comparing the percent soil removal soiled cloth, and the washed cloth, the results being Of these formulations with that Of the o n expressed as per cent soil removal. Because of variaformulationtions in degree and type of soiling, in water and i Detergency results obtained on a variety of the subl th, d other unknown i bl h art h d p ject compounds are given in the following table. Each o d th eth d f using l i detergency ratings value shown is the average of at least four tests. For f r c m i d t t ff ti comparison, the detergency rating is given for a linear The relative detergency ratings are obtained by comalkylbehzehe Sulfohate (L (having from 10 to 13 paring and correlating the per cent soil removal results Carbon Straight chain alkyl p both with and Withfrom solutions containing the detergents being tested out Phosphate builder (Sodium p yp p with the results from two defined standard solutions. Each tion tested Comprised 25 weight per- The two standard solutions are selected to represent a cent of the test material along with 1% y y detergent system exhibiting relatively high detersive Cellulose, 7% Sodium silicate, 8% water, and Suffieient characteristics and a system exhibiting relatively low Sodium sulfate to make 100% The LAS comparison detersive characteristics. The systems are assigned deformulations Were pr pared in he same way except tergency ti f 6,3 d 2,2, ti l that in Test 1 20% of LAS and 35% of sodium tripoly- By washing rtions of h il d l th i h h phosphate were used. The formulations were tested at standardized Solutions, as we as i h two test l a concentration in water of 0.10 and 0.15 weight percent. The test results were obtained at a pH of 9.5.

TABLE II DETERGENT EFFECTIVENESS RELATIVE DETERGENCY RATINGS TEST at 0.1% (Wt.) Conc. At 0.15% (Wt.) Conc. NO. COMPOUND 50 ppm ppm ppm 50 ppm 100 ppm 180 ppm TESTED 1 LAS with phosphate 5.8 3.9 1.7 6.3 6.2 4.1 2 LAS without phosphate 2.6 1.3 0.0 3.9 2 4 0.9 3 Product of Ex. No. 14 6.1 5.0 4 13 4.7 4.4 5 9 6.3 5.4 6 15 5.4 4.7 7 16 5.3 4.7 8 17 5.4 4.6 9 18 5.1 4.8 10 12 4.2 4.1 1 1 6 5.6 4.9 l2 19 5.3 4.8 3 9 5 8 5 4 4.9 13 20 5.0 4.8 14 22 5.3 15 30 5.5 2:3 16 29 5.6 4,

DETERG NT EFFECTIVENESS RELATIVE DETER'GENCY RATINGS TEST 1 at 0.1% (Wt.) Cone. At 0.15% (WL) Conc. NO. COMPOUND 50 ppm 100-.ppm 180 ppm 50 ppm 100 ppm 180 ppm TESTED 17 25 4.9 4.7 I8 24 3.6 r 4 4 19 26 5.4 4.8 20 27 5.6 5.1 2| 28 5.6 5.1 '22 34 5.4 4.8 .23 35 5.2 T 4.7

As can be seen from these data, the compositions of tration'with more than 50% .survival and the lowest this invention are highly effective as heavy duty launconcentration with less than 50% survival. dering agents. Their efiectiveness is comparable to It was found in these tests that those compounds conventional LAS with phosphate and surprisingly having central attachment of the succinic ester portIon more effective than LAS without phosphatebuilders. of the molecule to the hydrocarbyl chain were surpris- In order to determine the .toleranceof fish for the 20 ingly less toxic than the compounds having end chain detergent active compounds of this invention the folattachment. Table III contains data comparing the toxlowing routine bioassay method was employed: Stanicity .of compounds having central and end chain atdard Methods for the Examination of Water and Waste tachments. I

TABLE III FISH TOLERANCE TEST CENTRAL END CHAIN TL... N0. COMPOUND ATTACH.(%) ATTACH.( (PPM) TEST D l Product of Ex. No. 28 O 100 0.3 2 27 75 25 0.3 3 26 95 5 1.8 4 9 100 2.2 s 8 95 s 20.0 6 l4 0 I00 5.3 7 13. 9s 20 Water, American Public Health Association, pages Data from a representative number of other com- 458-471, 11th Edition (1960). The testis performed as pounds of this invention are set forth in the following follows: For each test concentration a S-gallon jar contable. These data are compared with the TL,, 96 values taining 10 liters of tap water dechlorinated by air blowfor LAS and other conventional detergents.

TABLE IV EIsH TOLERANCE NUMBER OF TEsT CARBON ATOMs IN TL,,,' NO. COMPOUND TESTED") HYDROCARBYL (PPM) CHAIN 8 LAS 10-13 3.2 9 LAS 11-14 1.6 10 Tallow alcohol sulfate 18 1.3 1 l Ethoxylated primary alcohol 14-15 3.] I2 Product of Ex. No. l0 17 56 13 6 18 3.5 14 II I9 I 15 15 I7 8.5 l6 I6 18 6.8 I7 17 I9 2.8 18 I9 16-18 8.0 I9 20 16-18 11.2 20 I7 4.2 2| 29 19 0.7 22 31 17 7.7 23 7 18 4.4 24 32 19 2.2

"All non-commercial compounds have about 91-95% central attachment, except test No 25 which has 83% Central attachment.

Commercial product.

"Run in 0 ppm hardness (otherwise precipitates with hardness).

ing was prepared. The test surfactant is added and 10 sticklebacks (Gasterosteidae) are transferred from a fresh water holding tank to the jar. Dead fish are counted and removed at 6 hours, 24 hours, 48 hours, 72 hours and 96 hours. The test concentrations are based on decilog intervals, and the 96-hour median tolerance limit ('IL is obtained for graphical or arithmetic interpolation between the highest concen- These data show that the TL, values for most of the compounds of this invention, particularly those having internal attachment are surprisingly higher than the linear alkylbenzene sulfonate. ,V

The degree of degradation under conditions such as are encountered in cesspools and septic tanks for the compounds of this invention were determined by tests set forth in Microaerophilic Biodegradation of Tallow-Based Anionic Detergents in River Water, E. W. Maurer, T. C. Crodon, and A. J. Stirton, The Utilization Res. Dev. Div., ARS, USDA, Philadelphia, Pennsylvania, JAOCS, Volume 48, Page 163 (1971). The microaerophilic test procedure described in this article was employed with the exception that a bacterial seed of filtered primary sewage anaerobic digester mix) was employed, the test was operated at room temperature and, in contrast to the results obtained by the authors, a small amount of degradation was observed in each case for linear alkylbenzene sulfonate.

Data in the following table show the degradation performance of the compounds of this invention in this test. The amount of surfactant in percent remaining after 2, 3, 5 and 6 days determined by standard methylene blue analysis is set forth.

TABLE V MICROAEROPHILIC TEST Percent Active Remaining After Elapsed Time Compound 2 Days 3 Days 5 Days 6 Days LAS 84 75 44 41 Product of Ex. No. I9 23 I3 7 7 12 metal salts such as inorganic sulfates, carbonates, or borates. Also nonphosphate builders may be included in the composition. Also small quantities of phosphate builders may be included in the compositions, although, of course, they are not necessary for effective de'tergency.

While the character of this invention has been described in detail with numerous examples, this has been done by way of illustration only and without limitation of the invention. It will be apparent to those skilled in the art that modifications and variations of the illustrative examples may be made in the practice of the invention within the scope of the following claims.

We claim:

1. A surface active compound of the formula in which R and R are substantially linear alkyl or alkenyl groups of 3 to 19 carbon atoms, R is alkylene of 2 to 4 carbon atoms, 14, v, x and y are 0 or 1, z is an integer l to 4, M is H or an alkali metal, alkaline earth metal, or ammonium cation, the sum of the carbon atoms in R and R is 13 to 21, the sum of the unsaturated sites in R and R is l, the sum of u and v is l, the sum ofx and y is l, and the sum ofu and x is 1.

2. The compound of claim 1 in which the sum of the carbon atoms in R and R is from 15 to 17.

3. The compound of claim 1 in which M is alkali metal.

4. The compound of claim 3 in which M is sodium. 

1. A SURFACE ACTIVE COMPOUND OF THE FORMULA
 2. The compound of claim 1 in which the sum of the carbon atoms in R1 and R2 is from 15 to
 17. 3. The compound of claim 1 in which M is alkali metal.
 4. The compound of claim 3 in which M is sodium. 